Determination of chlormequat chloride residues in animal derived foods by high performance liquid chromatography-tandem mass spectrometry

doi:10.3724/SP.J.1123.2019.04036

Abstract

Abstract:

A method for the determination of chlormequat chloride (CCC) residues in animal derived foods by high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was developed. The samples were extracted with acetonitrile containing 1% (v/v) acetic acid and defatted with n-hexane, followed by clean-up on a cationic solid phase extraction column. The analytes were separated on a Venusil MP C18(2) column (150 mm×2.1 mm, 3 μm) under a gradient elution program using acetonitrile and 0.1% (v/v) formic acid aqueous solution as the mobile phases. Then, the analytes were detected by tandem mass spectrometry using a positive electrospray ionization (ESI⁺) source in the multiple reaction monitoring (MRM) mode. Matrix-matched internal standard calibration curves were used for quantitative analysis. The calibration curves showed good linearity in the range of 0.200-500 μg/L for CCC, with correlation coefficients (r²) no less than 0.9993. The limit of quantification (LOQ) of the method was 0.500 μg/kg. The average recoveries of CCC in pork, beef, mutton, chicken, egg, pig kidney, beef liver, sheep kidney, chicken liver and milk matrices at spiked levels of 0.500-500 μg/kg were 93.4%-101%, and the relative standard deviations were 2.3%-8.0%. The method has less matrix interference, with high sensitivity, accuracy and reliability, and it is suitable for the quantitative detection of CCC residues in animal derived foods.

Key words: high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS), solid phase extraction (SPE), chlormequat chloride (CCC), animal derived foods

XIAO Yong, WU Haizhi, YUAN Liejiang, TANG Jiwang, WANG Shuxia, WANG Xiu, DENG Hang, WU Lin. Determination of chlormequat chloride residues in animal derived foods by high performance liquid chromatography-tandem mass spectrometry[J]. Chinese Journal of Chromatography, 2020, 38(2): 218-223.

Figures/Tables 6

Fig. 1 Molecular structure formula of chlormequat chloride (CCC)

Table 1 MS parameters of CCC and CCC-D4

Analyte	Monitoring ion pair (m/z)	Collision energy/eV	Tube lens offset/V
* Quantitative ion.
CCC	122.044＞58.077^*	23	51
	122.044＞62.993	21	51
	124.037＞58.045	28	52
CCC-D4	126.123＞58.157^*	26	58
	126.123＞67.111	22	58

Fig. 2 Chromatograms of CCC (0.500 μ g/kg) spiked in egg samples using the different chromatographic columns a. column: Venusil MP C18(2) (150 mm×2.1 mm, 3 μ m); mobile phase: (A) 0.1% (v/v) formic acid aqueous solution (containing 10 mmol/L ammonium acetate) and (B) acetonitrile; gradient elution program: 0-1.00 min, 10%B; 1.00-3.50 min, 10%B-95%B; 3.50-4.00 min, 95%B; 4.00-4.01 min, 95%B-10%B; 4.01-5.00 min, 10%B. b. column: Venusil HILIC (150 mm×2.1 mm, 3 μ m); mobile phase: 0.1% (v/v) formic acid aqueous solution (containing 10 mmol/L ammonium acetate)-acetonitrile (40 : 60, v/v); isocratic elution. c. column: Thermo Hypersil Gold (150 mm×2.1 mm, 3 μ m). Mobile phases and gradient elution program were the same as that in Fig. 2a.

Fig. 3 Effects of different elution solutions on the recoveries of CCC A. methanol (containing 50 mmol/L ammonium acetate); B. methanol (containing 75 mmol/L ammonium acetate); C. methanol (containing 100 mmol/L ammonium acetate); D. 50% (v/v) methanol aqueous solution (containing 100 mmol/L ammonium acetate); E. 80% (v/v) methanol aqueous solution (containing 100 mmol/L ammonium acetate).

Table 2 Linear equations, correlation coefficients (r2), LOQs, spiked recoveries and precisions of CCC in the different matrices (n=6)

Matrix	Linear equation	r²	LOQ/ (μg/kg)	Recoveries/%			RSDs/%
Matrix	Linear equation	r²	LOQ/ (μg/kg)	Low	Medium	High	Low	Medium	High
Low, medium, high spiked levels: 0.500, 10.0, 200 μ g/kg for pork, beef, mutton; 0.500, 5.00, 40.0 μ g/kg for chicken; 0.500, 10.0, 100 μ g/kg for egg, chicken live; 0.500, 20.0, 500 μ g/kg for pig kidney, beef liver, sheep kidney, milk; y: peak area ratio of CCC to CCC-D4; x: mass concentration, μ g/L.
Pork	y=0.0740+0.0955x	0.9999	0.500	99.6	95.8	95.6	4.2	4.1	3.2
Beef	y=0.0590+0.0961x	0.9999	0.500	97.5	99.4	93.7	6.7	6.7	3.5
Mutton	y=0.0732+0.0903x	0.9998	0.500	95.6	95.4	98.3	5.4	2.7	4.4
Chicken	y=0.0890+0.0926x	0.9993	0.500	95.9	97.8	96.5	5.4	5.8	3.5
Egg	y=0.0741+0.0911x	0.9999	0.500	99.9	101	97.3	3.5	2.8	2.6
Pig kidney	y=0.1024+0.0864x	0.9998	0.500	99.3	99.0	97.4	4.7	5.1	4.3
Beef liver	y=0.0744+0.0834x	0.9993	0.500	97.2	98.5	93.4	8.0	4.5	4.4
Sheep kidney	y=0.1545+0.0870x	0.9998	0.500	99.2	96.6	96.6	3.9	4.5	5.6
Chicken liver	y=0.0855+0.0881x	0.9999	0.500	99.3	100	98.7	6.1	3.6	3.4
Milk	y=0.0783+0.0909x	0.9995	0.500	98.8	98.4	99.3	5.6	4.7	2.3

Fig. 4 Chromatograms of CCC (0.500 μ g/kg) spiked in the different samples

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